Interpretation of the soret band of porphyrins based on the polarization spectrum of N-methyltetraphenylporphin fluorescence

Low-temperature (77 K) absorption, fluorescence, and fluorescence-excitation spectra and the fluorescence polarization spectrum for N-methyl-meso-tetraphenylporphin (N-methyl-TPP) are measured. Based on the polarization spectrum the absorption spectrum in the visible region (a “generic” porphyrin spectrum) is interpreted. In particular, it is shown that the fifth absorption band (the “Longo band”) that manifests itself in some porphyrins is a Q_y(0–2) band and does not belong to the individual electron transition. Emphasis is placed on the region of the Soret band. It is inferred that at least two allowed electron transitions (G →B_x and G→B_y) polarized mutually perpendicularly manifect themselves in this region. The interpretation of the Soret band of porphyrins [2] that attributes this band to one electron transition G→B_x is thereby rejected. This interpretation is confirmed by computer modeling of the polarization spectrum. Special features of the experimental polarization spectrum are explained by a more developed vibrational structure and, possibly, a larger half-width of the B_x band than the half-width of the B_y band. The contribution of the states of intramolecular charge transfer to the formation of the Soret band is discussed. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 1, pp. 65–72, January–February, 1999.     

Spectral fluorescence and polarization characteristics of <Emphasis Type="Italic">Z,Z</Emphasis>-bilirubin IXα

We have studied the spectral fluorescence and polarization characteristics of Z,Z-bilirubin IXα, at room temperature in chloroform and in aqueous buffer medium, within an equilibrium complex with human serum albumin (HSA), and also under low temperature conditions (T = −100°C) in isobutyl alcohol. We have observed a bathochromic shift of the fluorescence spectra, which is most pronounced for the bilirubin-albumin complex. The following are considered as possible reasons for the observed dependence of the position of the fluorescence (fluorescence excitation) spectra on the excitation (detection) wavelength: structural and spectral differences between the chromophores making up the bilirubin molecule; conformational heterogeneity of the pigment in solution; a contribution to the fluorescence from molecules which have not completed the vibrational relaxation process; inhomogeneous orientational broadening of the levels; heterogeneity of the microenvironment of the chromophores in the protein matrix. We show that polarized fluorescence of bilirubin occurs at room temperature, due to the anomalously short fluorescence lifetime τ (picosecond or subpicosecond ranges). Despite such a short τ, the absorption and emission polarization spectra suggest the presence of intramolecular nonradiative singlet-singlet energy transfer when bilirubin is excited to high vibrational sublevels of the S₁ state (degree of polarization p = 0.11–0.12). When fluorescence is excited on the long-wavelength slope of the absorption band, no transfer occurs: the degree of polarization (p = 0.46−0.47) is close to the limiting value (p = 0.50). We discuss the question of the role played by exciton interactions between chromophores in the bilirubin molecule when it is excited. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 1, pp. 108–119, January–February, 2007.     

Luminescence of biologically active 24-epicastasterone and a model compound

Biologically active brassinosteroid 24-epicastasterone, ring B of which contains a C=O group and has the nπ*-configuration for a low-lying electronic excited state, exhibits rapid fluorescence. The wavelengths of the fluorescence maxima of the steroid dissolved in hexane and acetonitrile are equal to 332 and 394 nm, respectively. The fluorescence lifetime of the steroid dissolved in acetonitrile is τ = 9.9 nsec. Solutions of 24-epibrassinolide do not luminesce. The long-wavelength electronic absorption band λ_max^abs = 340 nm in the absorption spectrum of an ethanol solution of model compound 2, ring D of which contains a C=O group π*-conjugated with the C=C double bond of ring C, like in the spectrum of the steroid, has a low extinction coefficient. An ethanol solution of 2 does not fluoresce. 24-Epicastasterone at 77 K in ethanol solution exhibits phosphorescence with λ_max^phos = 447 nm. The phosphorescence decay is exponential with τ = 0.79 msec. Compound 2 also phosphoresces. The phosphorescence spectrum of its ethanol solution has a maximum at 490 nm. The phosphorescence decay is nonexponential in the early stage. The phosphorescence lifetime is 25 msec in the exponential decay region. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 2, pp. 182–186, March–April, 2008.     

Transformation of radiation-induced defects responsible for theF-band of absorption in NaF crystals subjected to irradiation with light and annealing

It has been found that the F-band of optical absorption which is observed in ψ-irradiated NaF crystals consists of three overlapping bands. The band at 345 nm of width 40 nm is independent of the impurity composition of the crystals; it disappears upon exposure to radiation at 345 nm and appears again upon annealing at 460±15 K for 15 min. This band is correlatable in intensity with the superfine structure of an EPR spectrum. The width (65–110 nm) and the spectral position (355–375 nm) of the second band depend on the impurity composition of the crystal. The band of width 90–110 nm at 320–325 nm disappears upon annealing and appears after exposure to light simultaneously with the disappearance of an EPR signal. It is established that the band at 345 nm is caused by quasimolecules based on fluorine atoms, that at 355–375 nm is triggered by F-centers with a different impurity composition near the haloid vacancy, and the band at 320–325 nm owes its appearance to F-centers in a negatively charged state (F′). Institute of Molecular and Atomic Physics, National Academy of Sciences of Belarus, 70 F. Skorina Ave., Minsk, 220072, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 6, pp. 849–853, November–December, 1999.     

Fluorescence and absorption of polystyrene exposed to UV laser radiation

We show that when polystyrene is exposed (for 15–60 sec) to a UV laser light beam (λ = 248 nm), its absorption and luminescent properties change significantly. In the irradiated polymer, optical centers are formed with absorption bands in the 280–460 nm region and fluorescence bands in the 330–520 nm region. We have established the chemical structure of the optical centers for fluorescence of polystyrene. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 1, pp. 54–58, January–February, 2006.     

Influence of the mineral component in biotissues affected by calcinosis on their laser-induced fluorescence spectrum

Laser-induced fluorescence (LIF) spectra of human cardiac-valve tissues affected by calcinosis and of macroscopic calcinosis formations produced from resected cardiac valves with such pathology were investigated by comparison with analogous spectra of bone and myocardial tissue of an animal, LIF was excited by an excimer laser with λ=248 nm. In the spectrum of macroscopic calcinosis formations, luminescence bands of the mineral component were separted from the band of protein tissues when these tissues were subjected to heat treatment at 700°C. The investigations have shown that the LIF spectrum of a calcified tissue contains fluorescence bands of tryptophan and fluorescence bands of the mineral component (hydroxylapatite). A change in the spectrum of tissues with pathological processes can be cause not only by a relative change in the concentration of collagen elastin, but also by the additional fluorescenced of the hydroxylapatite mineral that is absent in a healthy cardiac tissue. It was found that the change in the spectrum characterized by the ratio of the LIF intensity at λ=330 nm to the LIF intensity at λ=450 nm is sufficiently large. This makes it possible to use measurements of the relative intensity of fluorescence at these wavelengths to control the degree of calcination of cardiac tissue. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 6, pp. 846–849, November–December, 1999.     

Stress-Induced Alteration of Chlorophyll Fluorescence Polarization and Spectrum in Leaves of <Emphasis Type="Italic">Alocasia macrorrhiza</Emphasis> L. Schott

The value of intrinsic chlorophyll fluorescence polarization, and the intensity in emission spectrum were investigated in leaf segments of Alocasia macrorrhiza under several stress conditions including different temperatures (25–50°C), various concentrations of NaCl (0–250 mM), methyl viologen (MV, 0–25 μM), SDS (0–1.0%) and NaHSO₃ (0–80 μM). Fluorescence emission spectrum of leaves at wavelength regions of 500–800 nm was monitored by excitation at 436 nm. The value of fluorescence polarization (P value), as result of energy transfer and mutual orientation between chlorophyll molecules, was determined by excitation at 436 nm and emission at 685 nm. The results showed that elevated temperature and concentrations of salt (NaCl), photooxidant (MV), surfactant (SDS) and simulated SO₂ (NaHSO₃) treatments all induced a reduction of fluorescence polarization to various degrees. However, alteration of the fluorescence spectrum and emission intensity of F₆₈₅ and F₇₃₁ depended on the individual treatment. Increase in temperature and concentration of NaHSO₃ enhanced fluorescence intensity mainly at F₆₈₅, while an increase in MV concentration led to a decrease at both F₆₈₅ and F₇₃₁. On the contrary, NaCl and SDS did not cause remarkable change in fluorescence spectrum. Among different treatments, the negative correlation between polarization and fluorescence intensity was found with NaHSO₃ treatments only. We concluded that P value being measured with intrinsic chlorophyll fluorescence as probe in leaves is a susceptible indicator responding to changes in environmental conditions. The alteration of P value and fluorescence intensity might not always be shown a functional relation pattern. The possible reasons of differed response to various treatments were discussed.     

Absorption,fluorescence, and fluorescence excitation spectra of free molecules of indole and its derivatives

We have obtained and analyzed the absorption, fluorescence, and fluorescence excitation spectra of indole vapor, N-acetyl-L-tryptophan vapor, and 3-indole aldehyde vapor. From analysis of the dependence of the fluorescence spectrum of the free indole molecules on the wavelength of the exciting radiation λ_ex, it follows that emission of fluorescence occurs when the molecules undergo a transition from the one electronically excited state ¹L_b. The fluorescence spectra of the studied compounds are insignificantly different, suggesting a major role for the indole chromophore in formation of the compounds. The absorption spectrum of N-acetyl-L-tryptophan, in which the group of atoms is added to the indole ring through a-C-C bond, is similar to the spectrum of indole, while the spectrum of 3-indole aldehyde is significantly different from the indole spectrum due to the effect of the C=O group conjugated with the indole ring. The fluorescence excitation spectra are considerably different from the absorption spectra. This is associated with the strong dependence of the quantum yield for the free molecules on λ_ex. Qualitatively, they are mirror-symmetric to the fluorescence spectra of the stodied compounds. Analysis of the data obtained provides a basis for assuming that in the case of free molecules of indole and its derivatives, the ¹L_a absorption in the extreme long-wavelength region of the spectrum does not overlap ¹L_b absorption. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 2, pp. 218–222, March–April, 2007.     

Characteristic features of thermoluminescence kinetics in dosimetric aluminum oxide crystals

We have studied the thermoluminescence curves in the 420 nm band (F centers) and the 330 nm band (F⁺ centers) within the temperature range of the dosimetric peak (T_max = 450 K) in anion-deficient aluminum oxide crystals. Assuming general-order kinetics, we have analyzed the thermoluminescence decay curves on the rising and falling sides of the dosimetric peak, in samples with different degrees of deep trap filling. We have established differences in the order of the kinetics within different temperature ranges of the dosimetric peak. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 2, pp. 187–190, March–April, 2006.     

Solution electronic spectra of brassinosteroid and a synthesized conjugate of a steroid and a fluorescent label

Electronic absorption spectra of 24-epicastasterone and 24-epibrassinolide solutions have been recorded and analyzed. The long-wavelength band in solution spectra of the former steroid with maxima in the region 292–286 nm is assigned to the electronic nπ*-transition of a carbonyl chromophore. The latter steroid contains an O-C=O group, for which the extinction coefficient in this spectral region is approximately one order of magnitude less. These differences can be used to identify the studied steroids. A method to synthesize the conjugate of 24-epicastasterone with a fluorescent label, dansylhydrazine, which shows intense fluorescence and absorption, is described. Absorption spectra of the label and conjugate in diethylether, tetrahydrofuran, ethanol, and acetonitrile solutions are practically independent of the solvent properties. The exceptions are solutions of the conjugate in hexane and water. All investigated solutions of label and conjugate show intense fluorescence. As the dielectric constant of the solvent increases, the fluorescence spectra shift to long-wavelength. The fluorescence energetic and time characteristics of both the label and conjugate are similar, which enables the conjugate to be used in developing a method for immunofluorescent analysis of the brassinosteroid 24-epicastasterone. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 1, pp. 74–78, January–February, 2008.     

Spectral and kinetic properties of fluorescence of immunoactive steroids in the gas phase

We have used steady-state fluorescence spectroscopy and pulsed kinetic fluorimetry with high time resolution to experimentally study the spectral and temporal characteristics of luminescence of immunoactive 8-aza-D-homogona-1,3,5(10), 13-tetraene-12,17a-dione (8-aza-D-homogonane) molecules in the gas phase. We have established the existence of several centers emitting long-wavelength and short-wavelength fluorescence. The fluorescence of high-temperature 8-aza-D-homogonane vapor (T = 550 K) when excited by radiation with λ_ex = 266 nm is represented by two spectrally separated emission bands with maxima λ _max ^fl = 465 nm and λ _max ^fl = 365 nm. Analysis of the distribution of fluorescence decay times for 8-aza-D-homogonane showed that in the spectral range of the emission wavelengths 360–590 nm, the fluorescence decay kinetics contains three components with average lifetimes <200 psec, 2.8 nsec and 13.5 nsec. The multicenter nature of luminescence of 8-aza-D-homogonane was confirmed by direct measurements of instantaneous fluorescence spectra in different stages of luminescence decay. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 3, pp. 309–314, May–June, 2006.     

Spectral luminescence properties of hydroporphyrazine metallo complexes

We have studied the spectral luminescence properties of a zinc complex of dibenzobarreleno-substituted tetraazaisobacteriochlorin (a synthetic tetrapyrrole pigment which is the structural analog of the biologically important chromophore isobacteriochlorin) and a palladium complex of dibenzobarreleno-substituted tetraazachlorin. We have shown that despite the substantial effect of aza-substitution on the electronic structure and the electronic spectra of the tetrapyrrole molecules, the effect of hydrogenation of adjacent pyrrole rings on the spectral luminescence properties is similar in compounds with nitrogen and carbon bridges. As in the free base case, the fluorescence of the studied zinc complex is strongly quenched at 293 K but flares up at 77 K (temperature and viscosity-dependent quenching). To study the substituted Zn-tetraazaisobacteriochlorin, we determined the position of the 0-0 band of the low-intensity transition S₀ → S₂ and showed that the S₂ → S₁ energy difference increases with bridge aza substitution. For the Pd complex of dibenzobarreleno-substituted tetraazachlorin, we could not detect phosphorescence in the near IR region (to 1150 nm); we detected weak fluorescence. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 5, pp. 700–707, September–October, 2008.     

Spectral-luminescence properties of a norbornene-substituted tetraazachlorin and its metal complexes

The spectral-luminescence properties of a tetraazachlorin derivative with a norbornene fragment annelated to a reduced pyrrole ring and its complexes with zinc and palladium have been studied at 293 and 77 K. For the norbornene-substituted free base, differences in fluorescence from unsubstituted tetraazachlroin and its dibenzobarrelene-substituted analog are found. The fluorescence lifetime is observed to rise by ∼7 times for the free base and by ∼1.6 ties for the Zn complex on going from 293 to 77 K. An essential dependence of the photophysical parameters on the nature of the solvent is noted. The fluorescence polarization spectrum of the norbornene-substituted tetraazachlorin reveals in the Soret band region at least four electronic transitions. For the Pd complex, weak phosphorescence in the near IR region has been detected; the 0–0 band maximum is at 990 nm and the singlet–triplet interval amounts to 5800 cm^–1, which is larger by 400 cm^–1 than for Pd tetraazaporphine. The quantum yields of the photosensitized formation of singlet oxygen have been determined using a relative luminescence method.     

Spectral Properties of Thioflavin T and Its Complexes with Amyloid Fibrils

Comparative analysis of the absorption and fluorescence spectra and fluorescence excitation spectra of thioflavin T (ThT) in various solvents and in the composition of amyloid fibrils has shown that ThT, when excited in the region of the long-wavelength absorption band, fluoresces in the spectral region with a maximum at 478–484 nm. The appearance in aqueous and alcohol solutions of a fluorescence band with a maximum near 440 nm has been attributed to the presence in the composition of the ThT preparations of an impurity with an absorption band in the 340–350-nm range. The literature data showing that in glycerol ThT has a wide fluorescence spectrum with two maxima are due to the artifact connected with the use of a high concentration of the dye. It has been suggested that the cause of the low quantum yield of ThT aqueous and alcohol solutions is the breakage of the system of conjugated bonds due to the reorientation of the benzothiozole and benzaminic rings of ThT in the excited state with respect to one another. The main factor determining the high quantum yield of fluorescence of ThT incorporated in fibrils is the steric restriction of the rotation of the rings about one another under these conditions. The suggestions made have been verified by the quantum-chemical calculation of the ThT molecule geometry in the ground and excited states.     

Manifestation of vibronic intensity borrowing in fluorescence spectra of metalloporphyrins

In selective laser excitation and at T=4.2 K, fine-structure spectra of the fluorescence of the complexes of Mg, Zn, In, and TiO with octaethylporphyrin are obtained. It is shown that the fine-structure fluorescence spectra of these compounds are formed to a large aegree by ribronic interaction between quasi-degenerate S₁ and S₂ electron states. An increase in the relative intensities of a number of negatively polarized fluorescence lines in displacement of the excitation line from a longwave edge of the band of an S₀→S₁ transition in the shortwave direction is revealed. Reported at the VIIIth International Conference on Spectroscopy of Porphyrins and Their Analogs, Minsk, September 22–26, 1998. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 4, pp. 518–522, July–August, 1999.     

Synthesis of w-CdS quantum dots and discovery of intense sub band emission owing to longitudinal optical phonons

Cadmium sulfide (CdS) quantum dots (QDs), capped with cetyltrimethylammonium bromide (CTAB), and was synthesized as stable, aqueous, colloidal nanofluid. A series of nine intense, well-resolved emission lines between 400 and 750 nm were observed for the first time when exciting the CdS QDs nanofluid with a 355-nm high energy pulsed Nd:YAG laser radiation. The energy separation between any two successive emission lines equals to the characteristic overtone energy of 295 cm⁻¹ of the longitudinal optical phonon of CdS QDs. In addition, recording the PL spectrum by using a xenon broad band light source resulted in the observation of this characteristic overtone energy of 295 cm⁻¹. In agreement with this photoluminescence characteristic, Raman spectrum exhibited four prominent Stokes lines with Raman shift equal to and multiple of 295 cm⁻¹. Transmission electron microscopy investigation showed that the CdS QDs were spherical with hexagonal wurtzite structure and had a size in the range of 5–10 nm.     

Spectral characteristics of heterocyclic compounds with a chain structure, cooled in an ultrasonic jet

We have recorded the fluorescence excitation spectra of three heterocyclic compounds with a chain structure [BPO (2-phenyl-5-(4-diphenylyl)oxazole), POPOP (1,4-di[2-(5-phenyloxazolyl)]benzene, and TOPOT (1,4-di[2-(5-n-tolyloxazolyl)]benzene] and the fluorescence spectra of POPOP, under conditions where the molecules were cooled in an ultrasonic helium jet. A line structure is observed in the spectra of POPOP and TOPOT; for the BPO molecules, whose configuration changes considerably during electronic excitation, vibrational structure is apparent only in the low-frequency region of the excitation spectrum, and a diffuse spectrum is recorded starting from ν ₀ ⁰ + 200 cm⁻¹. For all the compounds, in the spectra we recorded vibrations with frequencies up to 100 cm⁻¹, arising due to the flexibility of the molecular structure. The rotational contours of the lines for the electronic and vibronic transitions of the POPOP molecules (T_rot = 10.5 K) and TOPOT molecules (T_rot = 15 K) are structureless and bell-shaped. The degree of polarization of the fluorescence P_fl for the jet-cooled POPOP molecules for excitation of vibrations along the absorption band up to 2000 cm⁻¹ above ν ₀ ⁰ is practically constant (∼8.4%) and matches P_fl for high-temperature vapors. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 6, pp. 728–734, November–December, 2006.     

Radiative characteristics and kinetics of processes in low-pressure gas-discharge lamps based on a mixture of helium and iodine vapors

The UV radiation of glow- and capacitive-discharge lamps based on mixtures of inert gases with iodine vapors are optimized in the spectral range of 175–360 nm, in which working helium-iodine mixtures of different compositions are used. The most intense spectral lines in the bactericidal region of the spectrum were the atomic lines of iodine (183.0, 206.2 nm), and in the region of 320–360 nm, emission of the spectral band of an iodine molecule prevailed with a maximum at λ = 342 nm. For a capacitive lamp with a casing opaque in the spectral range λ < 250 nm, the main part of the plasma emission power is concentrated in the A′-D′ band of an iodine molecule with a maximum at 342 nm. The emission brightness of this lamp is optimized in iodine molecule transitions depending on the partial helium pressure. We present the results of simulating the kinetics of processes in a glow-discharge plasma in mixtures of He, Xe, and iodine vapors. We establish the dependence of the main part of the emission intensity of the 206.2 nm spectral line of an iodine atom and the 342 nm band of an iodine molecule on the helium pressure in a glow-discharge lamp operating on a He-I₂ mixture.     

Electronic absorption and emission spectra of Alq3 in solution with special attention to a delayed fluorescence

Tris(8-quinolinolato)aluminum(III) (Alq₃) shows electronic absorption bands at 378, 360 (in a 1:1 mixed solvent of methanol and ethanol (ME) at 77 K), 334, 316, 300, 263, 255.8, and 233 nm in ethanol at room temperature. According to the polarized fluorescence excitation spectrum together with MO calculations, for instance, the 360 nm band is assigned to an LL CT transition (an intramolecular charge transfer transition between two ligands), and the 378 nm band to an LM/ML CT one (an intramolecular charge transfer transition between ligand and metal). Alq₃ shows a broad fluorescence band peaking at around 478 nm in the ME matrix at 77 K. The emission spectrum measured with a phosphoroscope has two emission bands at 567 and 478 nm. The 567 nm band accompanies vibronic bands at 578 and 605 nm, being safely assigned to a phosphorescence of Alq₃. The lifetimes of the 478 and 567 nm bands are both 5.4 ms. The lifetime of the 478 nm band together with the band position and its band shape indicate that this band can be assigned to a delayed fluorescence.     

一种基于荧光信号的海面厚油膜评估方法

油膜厚度是海面溢油污染评估分析的一个重要指标,激光诱导荧光(LIF)技术是目前最有效的海面溢油探测技术之一,基于LIF探测技术的油膜厚度反演算法当下仅有适用于薄油膜(≤10~20 μm)的评估方法,而对于较厚油膜(>20 μm)的评估目前尚无有效的反演算法。鉴于此,提出一种基于LIF技术适用于较厚油膜的反演算法,该算法采用油膜荧光信号反演油膜厚度,推导了油膜厚度反演公式,并给出了基于该反演算法的油膜厚度评估方法。首先采用最大类间方差算法(Otsu)选取合适的荧光光谱波段,然后根据选取波段内每个波长的光谱数据反演油膜厚度,最后采用反演油膜厚度的平均值作为油膜厚度评估结果。研究了该算法的适用范围,给出了该算法有效评估范围最大值与测量相对误差的关系,并结合消光系数给出了在多种测量误差条件下不同消光系数油品有效评估范围的最大值。通过实验对本文方法进行了验证,选用原油和白油的混合油(1∶50)作为实验油品,以波长为405 nm的激光作为激发光源,采集波长范围为420～750 nm,采集了海水背景荧光和拉曼散射光光谱、实验油品的荧光特征光谱和多种不同厚度的较厚油膜的荧光光谱。采用Otsu算法选取420～476 nm波段评估油膜厚度,在实验油品油膜厚度≤800 μm时,该算法对油膜厚度的评估具有较高的精度,平均误差为10.5%;在油膜厚度>800 μm时,平均误差为28.8%,评估误差较大且随油膜厚度的增加快速变大,该实验结果与利用测量相对误差和消光系数的分析结果一致。实验结果表明,该方法可以实现对海面较厚油膜厚度的有效评估,并可以根据测量相对误差和消光系数判断评估结果的有效性。